Pracownicy

Streszczenie:
To date, Additive Manufacturing (AM) has come to the fore as a major disruptive technology embodying two main research lines – developing increasingly sophisticated printing technologies and new processable materials. The latter has fostered a tremendous leap in AM technological advancement, allowing 3D printing to play a central role in dictating the tailorable settings for material design. In particular, the manufacturing of three-dimensional (3D) objects with functional hierarchical porous structure is of the utmost importance for numerous research areas, including tissue engineering, catalysis, aerospace, environmental science, electrochemistry, energy and sound absorption and light engineering materials. Biphasic inks such as emulsions, foams, and solid dispersions represent viable templating systems to realise multiscale porosity. The combination of AM techniques and biphasic inks provide pivotal control over multiple levels of material structure and function, enabling the use of advanced materials with unprecedented 3D architectures as well as physical, chemical, and mechanical properties. The related potential benefits are significant, with functional perspectives for a wide variety of research fields. In this concise review, we provide an updated overview of the employment of biphase inks and show how they are adapted to different AM technologies or vice versa.

Streszczenie:
Here is reported an expedient synthesis implementing enabling technologies of a family of thiophene-based heptamers alternating electron donor (D) and acceptor (A) units in a D–A′–D–A–D–A′–D sequence. The nature of the peripheral A groups (benzothiadiazole vs. thienopyrrole-dione vs. thiophene-S,S-dioxide) and the strength of the donor units (alkyl vs. thioalkyl substituted thiophene ring) have been varied to finely tune the chemical-physical properties of the D–A oligomers, to affect the packing arrangement in the solid-state as well as to enhance the photovoltaic performances. The optoelectronic properties of all compounds have been studied by means of optical spectroscopy, electrochemistry, and density functional theory calculations. Electrochemical measurements and Kelvin probe force microscopy (KPFM) predicted a bifunctional behaviour for these oligomers, suggesting the possibility of using them as donor materials when blended with PCBM, and as acceptor materials when coupled with P3HT. Investigation of their photovoltaic properties confirmed this unusual characteristic, and it is shown that the performance can be tuned by the different substitution pattern. Furthermore, thanks to their ambivalent character, binary non-fullerene small-molecule organic solar cells with negligible values of HOMO and LUMO offsets were also fabricated, resulting in PCEs ranging between 2.54–3.96%.

Streszczenie:
Intrinsically conducting polymers (ICPs) are widely used to fabricate biomaterials; their application in neural tissue engineering, however, is severely limited because of their hydrophobicity and insufficient mechanical properties. For these reasons, soft conductive polymer hydrogels (CPHs) are recently developed, resulting in a water-based system with tissue-like mechanical, biological, and electrical properties. The strategy of incorporating ICPs as a conductive component into CPHs is recently explored by synthesizing the hydrogel around ICP chains, thus forming a semi-interpenetrating polymer network (semi-IPN). In this work, a novel conductive semi-IPN hydrogel is designed and synthesized. The hybrid hydrogel is based on a poly(N-isopropylacrylamide-co-N-isopropylmethacrylamide) hydrogel where polythiophene is introduced as an ICP to provide the system with good electrical properties. The fabrication of the hybrid hydrogel in an aqueous medium is made possible by modifying and synthesizing the monomers of polythiophene to ensure water solubility. The morphological, chemical, thermal, electrical, electrochemical, and mechanical properties of semi-IPNs were fully investigated. Additionally, the biological response of neural progenitor cells and mesenchymal stem cells in contact with the conductive semi-IPN was evaluated in terms of neural differentiation and proliferation. Lastly, the potential of the hydrogel solution as a 3D printing ink was evaluated through the 3D laser printing method. The presented results revealed that the proposed 3D printable conductive semi-IPN system is a good candidate as a scaffold for neural tissue applications.

Streszczenie:
The Coronavirus disease 2019 (COVID‐19) emergency has demonstrated that the utilization of face masks plays a critical role in limiting the outbreaks. Healthcare professionals utilize masks all day long without replacing them very frequently, thus representing a source of cross‐infection for patients and themselves. Nanotechnology is a powerful tool with the capability to produce nanomaterials with unique physicochemical and anti‐pathogen properties. Here, we outline how to realize non‐disposable and highly comfortable respirators with light‐triggered self‐disinfection ability by bridging bioactive nanofiber properties and stimuli‐responsive nanomaterials. The visionary road highlighted in this Concept is based on the possibility to develop a new generation of masks based on multifunctional membranes where the presence of nanoclusters and plasmonic nanoparticles arranged in a hierarchical structure enables the realization of a chemically‐driven and on‐demand anti‐pathogen activities. Multilayer electrospun membranes have the ability to dissipate humidity present within the mask, enhancing the wearability and usability. The photo‐thermal disinfected membrane is the core of these 3D printed and reusable masks with moisture pump capability. Personalized face masks with smart nano‐assisted destruction of pathogens will bring enormous advantages to the entire global community, especially for front‐line personnel, and will open up great opportunities for innovative medical applications.

Słowa kluczowe:
face masks, light-responsive nanomaterials, anti-pathogen, electrospinning, digitally personalized

Streszczenie:
In recent years, the main quest of science has been the pioneering of the groundbreaking biomedical strategies needed for achieving a personalized medicine. Ribonucleic acids (RNAs) are outstanding bioactive macromolecules identified as pivotal actors in regulating a wide range of biochemical pathways. The ability to intimately control the cell fate and tissue activities makes RNA-based drugs the most fascinating family of bioactive agents. However, achieving a widespread application of RNA therapeutics in humans is still a challenging feat, due to both the instability of naked RNA and the presence of biological barriers aimed at hindering the entrance of RNA into cells. Recently, material scientists’ enormous efforts have led to the development of various classes of nanostructured carriers customized to overcome these limitations. This work systematically reviews the current advances in developing the next generation of drugs based on nanotechnology-assisted RNA delivery. The features of the most used RNA molecules are presented, together with the development strategies and properties of nanostructured vehicles. Also provided is an in-depth overview of various therapeutic applications of the presented systems, including coronavirus disease vaccines and the newest trends in the field. Lastly, emerging challenges and future perspectives for nanotechnology-mediated RNA therapies are discussed.

Streszczenie:
A new side-chain C60-fullerene functionalized thiophene copolymer bearing tributylphosphine-substituted hexylic lateral groups was successfully synthesized by means of a fast and effective post-polymerization reaction on a regioregular ω-alkylbrominated polymeric precursor. The growth of the polymeric intermediate was followed by NMR spectrometry in order to determine the most convenient reaction time. The obtained copolymer was soluble in water and polar solvents and was used as a photoactive layer in single-material organic photovoltaic (OPV) solar cells. The copolymer photovoltaic efficiency was compared with that of an OPV cell containing a water-soluble polythiophenic homopolymer, functionalized with the same tributylphosphine-substituted hexylic side chains, in a blend with a water-soluble C60-fullerene derivative. The use of a water-soluble double-cable copolymer made it possible to enhance the control on the nanomorphology of the active blend, thus reducing phase-segregation phenomena, as well as the macroscale separation between the electron acceptor and donor components. Indeed, the power conversion efficiency of OPV cells based on a single material was higher than that obtained with the classical architecture, involving the presence of two distinct ED and EA materials (PCE: 3.11% vs. 2.29%, respectively). Moreover, the synthetic procedure adopted to obtain single material-based cells is more straightforward and easier than that used for the preparation of the homopolymer-based BHJ solar cell, thus making it possible to completely avoid the long synthetic pathway which is required to prepare water-soluble fullerene derivatives.

Słowa kluczowe:
water-soluble polymers, double-cable copolymers, polythiophenes, GRIM polymerization, tributylphosphine, water-soluble fullerenes, OPVs

Streszczenie:
The spread of antimicrobial resistance requires the development of novel strategies to combat superbugs. Bacteriolytic enzymes (enzybiotics) that selectively eliminate pathogenic bacteria, including resistant strains and biofilms, are attractive alternatives to antibiotics, also as a component of a new generation of antimicrobial wound dressings. AuresinePlus is a novel, engineered enzybiotic effective against Staphylococcus aureus—one of the most common pathogenic bacteria, found in infected wounds with a very high prevalence of antibiotic resistance. We took advantage of its potent lytic activity, selectivity, and safety to prepare a set of biodegradable PLGA/chitosan fibers generated by electrospinning. Our aim was to produce antimicrobial nonwovens to deliver enzybiotics directly to the infected wound and better control its release and activity. Three different methods of enzyme immobilization were tested: physical adsorption on the previously hydrolyzed surface, and covalent bonding formation using N-hydroxysuccinimide/N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide (NHS/EDC) or glutaraldehyde (GA). The supramolecular structure and functional properties analysis revealed that the selected methods resulted in significant development of nanofibers surface topography resulting in an efficient enzybiotic attachment. Both physically adsorbed and covalently bound enzymes (by NHS/EDC method) exhibited prominent antibacterial activity. Here, we present the extensive comparison between methods for the effective attachment of the enzybiotic to the electrospun nonwovens to generate biomaterials effective against antibiotic-resistant strains. Our intention was to present a comprehensive proof-of-concept study for future antimicrobial wound dressing development.

Słowa kluczowe:
antibacterial wound dressings, enzybiotic, fibers functionalization, electrospun wound dressings, Staphylococcus aureus

Streszczenie:
A new regioregular polythiophene derivative, called poly[3-(12-hydroxydodecyl)thiophene] (PT12OH), was synthesized by post-functionalizing its ω-brominated precursor poly[3-(12-bromododecyl)thiophene] (PT12Br) prepared using the Grignard metathesis route. Thanks to the optimal balance between hydrophilic and hydrophobic groups within its structure, PT12OH was highly soluble and easily filmable from common organic solvents allowing for its complete characterization. It also showed enhanced thermal properties, crystallinity, and self-assembling capabilities by the formation of strong inter- and intrachain hydrogen bonds. Bulk heterojunction photovoltaic cells with PT12OH and PC61BM showed a PCE of 4.83% and a remarkable over-time stability, offering good photoconversion efficiency even after 120 h of accelerated aging. Indeed, the PCE decrease was 34% for the hydroxylated polymer and 65% for its brominated precursor. It should also be pointed out that the enhanced thermal stability of PT12OH was achieved without resorting to any complex post-annealing photochemical, thermal, or chemical treatment and was thus directly ascribable to the polymer chemical structure. The simple and effective synthetic procedure, photovoltaic efficiency, and enhanced stability revealed the potential of PT12OH for large-scale organic solar cell applications.

Słowa kluczowe:
bulk heterojunction solar cell, regioregular polythiophene derivatives, post-polymerization functionalization, over-time stability

Streszczenie:
Thermoplasmonics deals with the generation and manipulation of nanoscale heating associated with noble metallic nanoparticles. To this end, gold nanoparticles (AuNPs) are unique nanomaterials with the intrinsic capability to generate a nanoscale confined light-triggered thermal effect. This phenomenon is produced under the excitation of a suitable light of a wavelength that matches the localized surface plasmonic resonance frequency of AuNPs. Liquid crystals (LCs) and hydrogels are temperature-sensitive materials that can detect the host AuNPs and their photo-induced temperature variations. In this perspective, new insight into thermoplasmonics, by describing a series of methodologies for monitoring, detecting, and exploiting the photothermal properties of AuNPs, is offered. From conventional infrared thermography to highly sophisticated temperature-sensitive materials such as LCs and hydrogels, a new scenario in thermoplasmonic-based, next generation, photonic components is presented and discussed. Moreover, a new road in thermoplasmonic-driven biomedical applications, by describing compelling and innovative health technologies such as on-demand drug-release and smart face masks with smart nano-assisted destruction of pathogens, is proposed. The latter represents a new weapon in the fight against COVID-19.Thermoplasmonics deals with the generation and manipulation of nanoscale heating associated with noble metallic nanoparticles. To this end, gold nanoparticles (AuNPs) are unique nanomaterials with the intrinsic capability to generate a nanoscale confined light-triggered thermal effect. This phenomenon is produced under the excitation of a suitable light of a wavelength that matches the localized surface plasmonic resonance frequency of AuNPs. Liquid crystals (LCs) and hydrogels are temperature-sensitive materials that can detect the host AuNPs and their photo-induced temperature variations. In this perspective, new insight into thermoplasmonics, by describing a series of methodologies for monitoring, detecting, and exploiting the photothermal properties of AuNPs, is offered. From conventional infrared thermography to highly sophisticated temperature-sensitive materials such as LCs and hydrogels, a new scenario in thermoplasmonic-based, next generation, photonic components is presented and discussed. Moreover, a new road in thermoplasmonic-driven biomedical applications, by describing compelling and innovative health technologies such as on-demand drug-release and smart face masks with smart nano-assisted destruction of pathogens, is proposed. The latter represents a new weapon in the fight against COVID-19.

Streszczenie:
Multifunctional nanomaterials with the ability torespond to near-infrared (NIR) light stimulation are vital for thedevelopment of highly efficient biomedical nanoplatforms with apolytherapeutic approach. Inspired by the mesoglea structure ofjellyfish bells, a biomimetic multifunctional nanostructured pillowwith fast photothermal responsiveness for NIR light-controlled on-demand drug delivery is developed. We fabricate a nanoplatformwith several hierarchical levels designed to generate a series ofcontrolled, rapid, and reversible cascade-like structural changesupon NIR light irradiation. The mechanical contraction of thenanostructured platform, resulting from the increase of temper-ature to 42°C due to plasmonic hydrogel−light interaction, causesa rapid expulsion of water from the inner structure, passing through an electrospun membrane anchored onto the hydrogel core. Themutual effects of the rise in temperature and waterflow stimulate the release of molecules from the nanofibers. To expand thepotential applications of the biomimetic platform, the photothermal responsiveness to reach the typical temperature level forperforming photothermal therapy (PTT) is designed. The on-demand drug model penetration into pig tissue demonstrates theefficiency of the nanostructured platform in the rapid and controlled release of molecules, while the high biocompatibility confirmsthe pillow potential for biomedical applications based on the NIR light-driven multitherapy strategy.

Słowa kluczowe:
bioinspired materials, NIR-light responsive nanomaterials, multifunctional platforms, electrospun nanofibers, plasmonic hydrogel, photothermal-based polytherapy, on-demand drug delivery

Streszczenie:
This work describes the morphological, optical, and thermo‐optical properties of a temperature‐sensitive hydrogel poly(N‐isopropylacrylamide‐co‐N‐isopropylmethacrylamide) [P(NIPAm‐co‐NIPMAm]) film containing a specific amount of gold nanorods (GNRs). The light‐induced thermoplasmonic heating of GNRs is used to control the optical scattering of an initially transparent hydrogel film. A hydrated P(NIPAm‐co‐NIPMAm) film is optically clear at room temperature. When heated to temperatures over 37 °C via light irradiation with a resonant source (λ = 810 nm) to the GNRs, a reversible phase transition from a swollen hydrated state to a shrunken dehydrated state occurs. This phenomenon causes a drastic and reversible change in the optical transparency from a clear to an opaque state. A significant red shift (≈30 nm) of the longitudinal band can also be seen due to an increased average refractive index surrounding the GNRs. This change is in agreement with an ad hoc theoretical model which uses a modified Gans theory for ellipsoidal nanoparticles. Morphological analysis of the composite film shows the presence of well‐isolated and randomly dispersed GNRs. Thermo‐optical experiments demonstrate an all‐optically controlled light attenuator (65% contrast ratio) which can be easily integrated in several modern optical applications such as smart windows and light‐responsive optical attenuators.

Słowa kluczowe:
active plasmonics, gold nanorods, hydrogels, optical attenuators, optical transparency, plasmonic nanoparticles, polymers

Streszczenie:
The dynamics of highly flexible micro- and nano-filaments are important to a variety of biological, medical, and industrial problems. The filament configuration variation and cross-stream migration in a microchannel are affected by thermal fluctuations in addition to elastic and viscous forces. Here, hydrogel nano-filaments with small bending Young's moduli are utilized to elucidate the transitional behavior of elastic Brownian filaments in an oscillatory microchannel flow. A numerical model based on chain elastic dumbbells similar to the Rouse-Zimm model accounting for elastic, viscous, and random Brownian forces is proposed and implemented. In addition, a theoretical model to describe the average orientation–deformation tensor evolution for an ensemble of filaments in an oscillatory flow is proposed. The results are compared with the evolution observed in the experiments.

Streszczenie:
Body tissues and organs have complex functions which undergo intrinsic changes during medical treatments. For the development of ideal drug delivery systems, understanding the biological tissue activities is necessary to be able to design materials capable of changing their properties over time, on the basis of the patient's tissue needs. In this study, a nanofibrous thermal‐responsive drug delivery system is developed. The thermo‐responsivity of the system makes it possible to self‐regulate the release of bioactive molecules, while reducing the drug delivery at early stages, thus avoiding high concentrations of drugs which may be toxic for healthy cells. A co‐axial electrospinning technique is used to fabricate core–shell cross‐linked copolymer poly(N‐isopropylacrylamide‐co‐N‐isopropylmethacrylamide) (P(NIPAAm‐co‐NIPMAAm)) hydrogel‐based nanofibers. The obtained nanofibers are made of a core of thermo‐responsive hydrogel containing a drug model, while the outer shell is made of poly‐l‐lactide‐co‐caprolactone (PLCL). The custom‐made electrospinning apparatus enables the in situ cross‐linking of P(NIPAAm‐co‐NIPMAAm) hydrogel into a nanoscale confined space, which improves the electrospun nanofiber drug dosing process, by reducing its provision and allowing a self‐regulated release control. The mechanism of the temperature‐induced release control is studied in depth, and it is shown that the system is a promising candidate as a "smart" drug delivery platform.

Słowa kluczowe:
biomimetic nanomaterials, electrospun core–shell nanofibers, hierarchical nanostructures, smart drug delivery, thermo‐responsive hydrogels

Streszczenie:
The poor intrinsic mechanical properties of chitosan hydrogels have greatly hindered their practical applications. Inspired by nature, we proposed a strategy to enhance the mechanical properties of chitosan hydrogels by construction of a nanofibrous and cellular architecture in the hydrogel without toxic chemical crosslinking. To this end, electrospun nanofibers including cellulose acetate, polyacrylonitrile, and SiO2 nanofibers were introduced into chitosan hydrogels by homogenous dispersion and lyophilization. With the addition of 30% cellulose acetate nanofibers, the cellular structure could be maintained even in water without crosslinking, and integration of 60% of the nanofibers could guarantee the free-standing structure of the chitosan hydrogel with a low solid content of 1%. Moreover, the SiO2 nanofiber-reinforced chitosan (SiO2 NF/CS) three-dimensional (3D) matrices exhibit complete shape recovery from 80% compressive strain and excellent injectability. The cellular architecture and nanofibrous structure in the SiO2 NF/CS matrices are beneficial for human mesenchymal stem cell adhesion and stretching. Furthermore, the SiO2 NF/CS matrices can also act as powerful vehicles for drug delivery. As an example, bone morphogenetic protein 2 could be immobilized on SiO2 NF/CS matrices to induce osteogenic differentiation. Together, the electrospun nanofiber-reinforced 3D chitosan matrices exhibited improved mechanical properties and enhanced biofunctionality, showing great potential in tissue engineering.

Słowa kluczowe:
chitosan hydrogel, electrospun nanofiber, mechanical property, nanofibrous matrix, tissue engineering

Streszczenie:
Side‐chain C60‐fullerene functionalized alkylthiophene copolymers with different regioregularity and fullerene content are successfully synthesized using a simple and straightforward post‐polymerization functionalization procedure based on a Grignard coupling reaction. The products are employed as single materials in photoactive layers of organic photovoltaic solar cells. The use of double‐cable polymers allows an enhanced control on the nanomorphology of the active blend, reducing the phase‐segregation phenomena as well as the macroscale separation between the electron acceptor and donor components. With the insertion of a thin layer of gold nanoparticles between buffer and active layer of the cells, a conversion efficiency of 5.68% is obtained. Moreover, an increased stability over time is achieved when the copolymers are photocrosslinked immediately after the annealing procedure, leading to acceptable efficiencies even after 80 h of accelerated ageing, a key feature for widespread applicability of the prepared devices.

Słowa kluczowe:
conjugated polymers, fullerenes, functionalization of polymers, metathesis

Streszczenie:
Graphene-based materials have demonstrated high chemical stability and are very promising for protection against the corrosion of metal surfaces. For this reason, in this work, protective layers composed of graphene oxide, reduced graphene oxide and their mixtures were investigated, respectively, against the corrosion of the surface of lead induced by water drops. The materials were deposited on a Pb surface from their suspensions using a Meyer rod. The surface chemical composition, morphology and structure of the coatings were studied by X-ray photoemission spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM) and stylus profilometry. Moreover, a specific methodology based on the evolution of the water contact angle with time was used to evaluate the reactivity of the lead surface. The results show that the graphene-based materials can form an efficient barrier layer against the degradation of the Pb surface and that the degradation process induced by water is reduced by more than 70%. Moreover, unexpectedly, the best protective performance was obtained using graphene oxide as the coating.

Streszczenie:
Nanofibrous materials find a wide range of applications, such as vascular grafts, tissue-engineered scaffolds, or drug delivery systems. This phenomenon can be attributed to almost arbitrary biomaterial modification opportunities created by a multitude of polymers used to form nanofibers, as well as by surface functionalization methods. Among these applications, the hemostatic activity of nanofibrous materials is gaining more and more interest in biomedical research. It is therefore crucial to find both materials and nanofiber structural properties that affect organism responses. The present review critically analyzes the response of blood elements to natural and synthetic polymers, and their blends and composites. Also assessed in this review is the incorporation of pro-coagulative substances or drugs that can decrease bleeding time. The review also discusses the main animal models that were used to assess hemostatic agent safety and effectiveness.

Słowa kluczowe:
blood-biomaterial interactions, coagulation, electrospinning, nanofibers, platelets, hemorrhage

Streszczenie:
The current work studies the electrospun poly (vinyl alcohol) (PVA) nanofibers and its nanocomposites including nanohydroxy apatite (nHAp) and nHAp/cellulose nanofibers (CNFs), emphasizing the impact of nanofillers on the toughness of nanofibers. PVA nanofibers were incorporated with 10 wt% of nHAp and then various amounts of CNF were added to subsequent PVA/nHAp fibrous nanocomposites. The morphology of nonwoven mats was studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). While neat PVA nanofibers were smooth and uniform in thickness, the nanofiller loading resulted in thinner fibers with less uniformity. Furthermore, the thermal properties of the nonwoven network of fibers were characterized employing thermogravimetric analysis (TGA). Although the maximum loss mass temperature of PVA was partially reduced upon addition of nanofillers, the onset of decomposition was not altered. The mechanical characterizations were performed using static tensile and dynamic mechanical analysis (DMA). Compared to neat PVA mats, the tensile test of nanocomposites mats demonstrated the significant increase in Young's modulus; however, strain at break was dramatically reduced. In addition, the fracture work was assessed from the area under the stress-strain curve, which showed brittleness of fibrous nanocomposites due to the nanofiller incorporation. Field emission SEM (FE-SEM) was employed to scan the fracture surface of stretched fibers. The increase in modulus of electrospun mats was also shown by DMA in frequency mode. In parallel, both tensile test and DMA confirmed the change in fracture of PVA fibers from a tough to brittle mode, due to the nanofiller addition.

Słowa kluczowe:
electrospun nanocomposites, nanofillers, toughness, mechanical properties

Streszczenie:
Three regioregular thiophenic copolymers, characterized by a bromine atom or a C60-fullerene group at different molar ratios at the end of a decamethylenic plastifying side chain, have been successfully synthesized using a straightforward postpolymerization functionalization procedure based on a Grignard coupling reaction. Owing to their good solubility in common organic solvents, the products were fully characterized using chromatographic, spectroscopic, thermal, and morphological techniques and used as single materials in the photoactive layers of organic solar cells. The photoconversion efficiencies obtained with copolymers were compared with those of a reference cell prepared using a physical blend of the precursor homopolymer and [6,6]-phenyl-C61-butyric acid methyl ester. The best results were obtained with COP2, the copolymer with a 21% molar content of C60-functionalized side chains. The use of the double-cable polymer made possible an enhanced control on the nanomorphology of the active blend, thus reducing phase-segregation phenomena as well as the macroscale separation between the electron-acceptor and -donor components, yielding a power conversion efficiency higher than that of the reference cell (4.05 vs 3.68%). Moreover, the presence of the halogen group was exploited for the photo-cross-linking of the active layer immediately after the thermal annealing procedure. The cross-linked samples showed an increased stability over time, leading to good efficiencies even after 120 h of accelerated aging: this was a key feature for the widespread practical applicability of the prepared devices.

Streszczenie:
Materials for the treatment of cancer have been studied comprehensively over the past few decades. Among the various kinds of biomaterials, polymer-based nanomaterials represent one of the most interesting research directions in nanomedicine because their controlled synthesis and tailored designs make it possible to obtain nanostructures with biomimetic features and outstanding biocompatibility. Understanding the chemical and physical mechanisms behind the cascading stimuli-responsiveness of smart polymers is fundamental for the design of multifunctional nanomaterials to be used as photothermal agents for targeted polytherapy. In this review, we offer an in-depth overview of the recent advances in polymer nanomaterials for photothermal therapy, describing the features of three different types of polymer-based nanomaterials. In each case, we systematically show the relevant benefits, highlighting the strategies for developing light-controlled multifunctional nanoplatforms that are responsive in a cascade manner and addressing the open issues by means of an inclusive state-of-the-art review. Moreover, we face further challenges and provide new perspectives for future strategies for developing novel polymeric nanomaterials for photothermally assisted therapies.

Streszczenie:
The present study aims to theoretically model and verify the mechanical behavior of electrospun fibers of poly(vinyl alcohol) (PVA) reinforced by nanohydroxy apatite (nHAp) and cellulose nanofibers (CNF), the three composites designated as PVA/nHAp, PVA/CNF, and PVA/nHAp/CNF. Tensile tests and AFM nanoindentation studies were used to measure tensile modulus of electrospun scaffolds and single fibers respectively. Halpin–Tsai and Ouali models were applied to predict the stiffness of electrospun mats. Theoretical analysis according to the Halpin–Tsai model showed that CNF have no preferred orientation in the electrospun fibers, particularly at higher filler content. Additionally, this model provided a better prediction than Ouali model, especially at lower filler content. Theoretical models based on the geometry of an unit cell in open-cell structure such as honeycomb, tetrakaidecahedron and cube models simulate electrospun scaffolds. Among the structural models for analysis of porous scaffolds, the honeycomb model showed the best prediction, tetrakaidecahedron model—a moderate one, and cube model was the worst. In general, it was proved by both experiment and theory that the porous structure of electrospun mat caused significant modulus reduction of nanocomposites.

Słowa kluczowe:
Nanocomposites, Cellulose nanofibers, Electrospinning, Modulus

Streszczenie:
Over the past few decades, there has been strong interest in the development of new micro- and nanomaterials for biomedical applications. Their use in the form of capsules, particles or filaments suspended in body fluids is associated with conformational changes and hydrodynamic interactions responsible for their transport. The dynamics of fibres or other long objects in Poiseuille flow is one of the fundamental problems in a variety of biomedical contexts, such as mobility of proteins, dynamics of DNA or other biological polymers, cell movement, tissue engineering, and drug delivery. In this review, we discuss several important applications of micro and nanoobjects in this field and try to understand the problems of their transport in flow resulting from material-environment interactions in typical, crowded, and complex biological fluids. Our aim is to elucidate the relationship between the nano- and microscopic structures of elongated polymer particles and their flow properties, thus opening the possibility to design nanoobjects that can be efficiently transported by body fluids for targeted drug release or local tissue regeneration.

Streszczenie:
Two water-soluble regioregular poly(3-alkylthiophene)s, incorporating aminic groups at the end of the side chains, have been synthesized using a post-polymerization functionalization procedure on a ω-bromine substituted polyalkylthiophene. The high solubility of the obtained polymers in water allowed for the preparation of “green” bulk heterojunction solar cells which reached a power conversion efficiency of 4.85% when PC61BM was used as electron-acceptor material. Improved optical absorption and photocurrent have been obtained by interposing a layer of Ag nanoparticles between the buffer and the photoactive layer, leading to a final power conversion efficiency of 5.51%.

Słowa kluczowe:
Water-soluble polythiophene, Bulk heterojunction solar cell, Organic photovoltaic

Streszczenie:
Physical and chemical factors resulting from the sterilization methods may affect the structure and properties of the materials which undergo this procedure. Poly(l-lactide-co-glicolide) (PLGA) is commonly used for medical applications, but, due to its inadequate mechanical properties, it is not recommended for load-bearing applications. One of the methods for improving PLGA mechanical properties is addition of hydroxyapatite nanoparticles (nHAp). The aim of this study was to evaluate the effect of nanoparticles addition on PLGA structure and properties after gamma radiation. According to our results, reduction of the molecular mass caused by gamma radiation was lower for PLGA with nHAp addition. Differential scanning calorimetry (DSC) analysis indicates an increase of crystallinity caused both by nHAp and gamma radiation. The first phenomenon can be explained by heteronucleation, while the second one is most probably related to higher molecular mobility of degrading polymer. Moreover, addition of nanoparticles increases thermal stability and affects the Young's modulus changes after gamma radiation.

Streszczenie:
Highly efficient single-material organic solar cells (SMOCs) based on fullerene-grafted polythiophenes were fabricated by incorporating electrospun one-dimensional (1D) nanostructures obtained from polymer chain stretching. Poly(3-alkylthiophene) chains were chemically tailored in order to reduce the side effects of charge recombination which severely affected SMOC photovoltaic performance. This enabled us to synthesize a donor–acceptor conjugated copolymer with high solubility, molecular weight, regioregularity, and fullerene content. We investigated the correlations among the active layer hierarchical structure given by the inclusion of electrospun nanofibers and the solar cell photovoltaic properties. The results indicated that SMOC efficiency can be strongly increased by optimizing the supramolecular and nanoscale structure of the active layer, while achieving the highest reported efficiency value (PCE = 5.58%). The enhanced performance may be attributed to well-packed and properly oriented polymer chains. Overall, our work demonstrates that the active material structure optimization obtained by including electrospun nanofibers plays a pivotal role in the development of efficient SMOCs and suggests an interesting perspective for the improvement of copolymer-based photovoltaic device performance using an alternative pathway.

Streszczenie:
The recent progress in bioengineering has created great interest in the dynamics and manipulation of long, deformable macromolecules interacting with fluid flow. We report experimental data on the cross-flow migration, bending, and buckling of extremely deformable hydrogel nanofilaments conveyed by an oscillatory flow into a microchannel. The changes in migration velocity and filament orientation are related to the flow velocity and the filament's initial position, deformation, and length. The observed migration dynamics of hydrogel filaments qualitatively confirms the validity of the previously developed worm-like bead-chain hydrodynamic model. The experimental data collected may help to verify the role of hydrodynamic interactions in molecular simulations of long molecular chains dynamics.

Streszczenie:
The aim of this research was to study the effect of charge polarity applied to the spinning nozzle on the structure and properties of polycaprolactone/chitosan (PCL/CHT) blends, in particular the efficiency of further surface modification by chondroitin sulphate (CS). The observed differences in the morphology and properties of fibres formed at different polarities were interpreted in terms of molecular interactions occurring in the system. FTIR results indicate stronger PCL-chitosan interactions at negative polarity, resulting in lower PCL crystallinity and crystal size distribution determined by DSC, as well as lower wettability. The charge polarity influences PCL/CHT fibre morphology and tailors some of their properties, e.g. wettability, mechanical properties and the efficiency of surface modification. Better efficiency of CS attachment was observed at negative polarity using atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) is most probably related to higher chitosan content at the fibres' surface being attracted by the negative external potential.

Słowa kluczowe:
Polycaprolactone/chitosan nanofibres, Charge potential effect in electrospinning, Polycaprolactone-chitosan interactions

Streszczenie:
Water-soluble regioregular poly{3-[(6-sodium sulfonate)hexyl]thiophene} (PT6S) and poly{3-[(6-trimethylammoniumbromide)hexyl]thiophene} (PT6N) have been synthesized and employed both as photoactive layers for the assembling of “green” bulk-heterojunction organic solar cells and as charge-collection layers in a cell with “classic” architecture. While the photovoltaic performances obtained with the two aforementioned polymers were lower than the reference cell, their latter use allowed to notably increase the inherent J-V properties, leading to a considerable enhancement in the overall photovoltaic output. The power conversion efficiency of the optimized multilayer BHJ solar cell reached 4.78%, revealing a higher efficiency than the reference cell (3.63%).

Słowa kluczowe:
Water-soluble polymer, Polythiophene derivative, Bulk heterojunction, Organic photovoltaic, Interfacial layer

Streszczenie:
A novel thiophenic tetramer containing a cinnamate group in the side chain with a functionalization degree of 50% is reported. The tetramer was obtained by means of a simple and straightforward procedure involving the functionalization of a p-methoxyphenoxy substituted thiophenic precursor, which led to a soluble product with a good yield. The oligomer was fully characterized from a structural and chemical point of view and employed for the fabrication of small molecule organic solar cells exploiting the bulk heterojunction (BHJ) architecture. The presence of an UV-light sensitive group in the tetramer allowed the photocrosslinking of tetramer/PCBM blends, giving high values of photocurrent and conversion efficiency for the exposed samples. Moreover, the UV-treated devices showed improved stability, even upon heating for three days at 130 °C, thus confirming that photocrosslinking can strongly reduce phase segregation under severe operational conditions.

Słowa kluczowe:
electronic materials, polymers, fullerenes, nanostructures, electrical characterization, semiconductors

Streszczenie:
Composite nanofibers made of a polyaniline-based polymer blend and different thiol-capped metal nanoparticles were prepared using ex situ synthesis and electrospinning technique. The effects of the nanoparticle composition and chemical structure on the electrical properties of the nanocomposites were investigated. This study confirmed that Brust's procedure is an effective method for the synthesis of sub-10 nm silver, gold, and silver-gold alloy nanoparticles protected with different types of thiols. Electron microscopy results demonstrated that electrospinning is a valuable technique for the production of composite nanofibers with similar morphology and revealed that nanofillers are well-dispersed into the polymer matrix. X-ray diffraction tests proved the lack of a significant influence of the nanoparticle chemical structure on the polyaniline chain arrangement. However, the introduction of conductive nanofillers in the polymer matrix influences the charge transport noticeably improving electrical conductivity. The enhancement of electrical properties is mediated by the nanoparticle capping layer structure. The metal nanoparticle core composition is a key parameter, which exerted a significant influence on the conductivity of the nanocomposites. These results prove that the proposed method can be used to tune the electrical properties of nanocomposites.

Streszczenie:
Electrospinning of chitosan blends is a reasonable idea to prepare fibre mats for biomedical applications. Synthetic and natural components provide, for example, appropriate mechanical strength and biocompatibility, respectively. However, solvent characteristics and the polyelectrolyte nature of chitosan influence the spinnability of these blends. In order to compare the effect of solvent on polycaprolactone/chitosan fibres, two types of the most commonly used solvent systems were chosen, namely 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and acetic acid (AA)/formic acid (FA). Results obtained by various experimental methods clearly indicated the effect of the solvent system on the structure and properties of electrospun polycaprolactone/chitosan fibres. Viscosity measurements confirmed different polymer–solvent interactions. Various molecular interactions resulting in different macromolecular conformations of chitosan influenced its spinnability and properties. HFIP enabled fibres to be obtained whose average diameter was less than 250 nm while maintaining the brittle and hydrophilic character of the nonwoven, typical for the chitosan component. Spectroscopy studies revealed the formation of chitosan salts in the case of the AA/FA solvent system. Chitosan salts visibly influenced the structure and properties of the prepared fibre mats. The use of AA/FA caused a reduction of Young's modulus and wettability of the proposed blends. It was confirmed that wettability, mechanical properties and the antibacterial effect of polycaprolactone/chitosan fibres may be tailored by selecting an appropriate solvent system. The MTT cell proliferation assay revealed an increase of cytotoxicity to mouse fibroblasts in the case of 25% w/w of chitosan in electrospun nonwovens.

Słowa kluczowe:
chitosan, electrospinning, PCL/chitosan fibres, solvent system, chitosan salts

Streszczenie:
In this article, we report on the production by electrospinning of P3HT/PEO, P3HT/PEO/GO, and P3HT/PEO/rGO nanofibers in which the filler is homogeneously dispersed and parallel oriented along the fibers axis. The effect of nanofillers' presence inside nanofibers and GO reduction was studied, in order to reveal the influence of the new hierarchical structure on the electrical conductivity and mechanical properties. An in-depth characterization of the purity and regioregularity of the starting P3HT as well as the morphology and chemical structure of GO and rGO was carried out. The morphology of the electrospun nanofibers was examined by both scanning and transmission electron microscopy. The fibrous nanocomposites are also characterized by differential scanning calorimetry to investigate their chemical structure and polymer chains arrangements. Finally, the electrical conductivity of the electrospun fibers and the elastic modulus of the single fibers are evaluated using a four-point probe method and atomic force microscopy nanoindentation, respectively. The electrospun materials crystallinity as well as the elastic modulus increase with the addition of the nanofillers while the electrical conductivity is positively influenced by the GO reduction.

Słowa kluczowe:
electrospun composite nanofibers, poly(3-hexylthiophene), graphene oxide, electrical conductivity, mechanical properties

Streszczenie:
The role of mechanical properties is essential to understand molecular, biological materials, and nanostructures dynamics and interaction processes. Atomic force microscopy (AFM) is the most commonly used method of direct force evaluation, but due to its technical limitations this single probe technique is unable to detect forces with femtonewton resolution. In this paper we present the development of a combined atomic force microscopy and optical tweezers (AFM/OT) instrument. The focused laser beam, on which optical tweezers are based, provides us with the ability to manipulate small dielectric objects and to use it as a high spatial and temporal resolution displacement and force sensor in the same AFM scanning zone. We demonstrate the possibility to develop a combined instrument with high potential in nanomechanics, molecules manipulation and biological studies. AFM/OT equipment is described and characterized by studying the ability to trap dielectric objects and quantifying the detectable and applicable forces. Finally, optical tweezers calibration methods and instrument applications are given.

Słowa kluczowe:
optical trap, nanomanipulation, nanomechanics, femtonewton forces

Streszczenie:
Recent biomedical hydrogels applications require the development of nanostructures with controlled diameter and adjustable mechanical properties. Here we present a technique for the production of flexible nanofilaments to be used as drug carriers or in microfluidics, with deformability and elasticity resembling those of long DNA chains. The fabrication method is based on the core-shell electrospinning technique with core solution polymerisation post electrospinning. Produced from the nanofibers highly deformable hydrogel nanofilaments are characterised by their Brownian motion and bending dynamics. The evaluated mechanical properties are compared with AFM nanoindentation tests.

Correction: Hydrogel Nanofilaments via Core-Shell Electrospinning, Nakielski P., Pawłowska S., Pierini F., Liwińska W., Hejduk P., Zembrzycki K., Zabost E., Kowalewski T.A., PLOS ONE, ISSN: 1932-6203, DOI: 10.1371/journal.pone.0133458, Vol.10, No.7, pp.e0133458-1-2, 2015

Słowa kluczowe:
Gels, Nanomaterials, Atomic force microscopy, Polymerization, Bending, Mass diffusivity, Mechanical properties, Hydrodynamics

Streszczenie:
The aim of this study was to examine the role of the nanofillers spatial arrangement in the electrical properties of hybrid organic-inorganic fibers. In this paper, we have presented experimental results for preparation of fibers with a nanometric diameter based on a polyaniline/poly(ethylene oxide) doped blend and geomimetic chrysotile nanotubes. The nanostructured material was prepared using electrospinning techniques. Electrospun fibers made by pristine polymers and by the same blend loaded with carbon nanotubes were used as reference materials to compare the structural, and electrical properties of the novel organic-inorganic material. Generally, electrical properties were improved by the addition of materials that have high conductivity. Electrospun fibers filled with a traditional insulator like chrysotile have shown higher electrical conductivity than the pristine materials. In order to fully understand how structural variations impact upon the electrical conductivity the materials were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy (RS), differential scanning calorimetry (DSC) and four-point probe method. The results suggest that the occurred electrical conductivity gain could be attributed to parallel orientation of the chrysotile nanotubes and higher crystallinity induced by the one-dimensional nanostructured filler materials. The obtained results bring us one step closer to using intrinsically conducting polymers (ICPs) in the creation of functionalized polymeric nanocomposites for nanotechnology.

Słowa kluczowe:
Nanocomposites, Conductive polymer, Electrospinning, Chrysotile, Carbon nanotubes

Streszczenie:
In this article we demonstrate the use of a blend made of two regioregular polythiophenic derivatives, namely poly(3-methylthio)thiophene and poly(3-hexyl)thiophene, to obtain conductive traces by the simple laser exposure of their thin films to a suitable laser source. The polymeric blend was also tested as a photoactive layer for BHJ solar cells, showing an improved surface morphology and a wider absorption spectrum, thus resulting in an enhanced photovoltaic performance. In the standard condition normally used for the cell preparation, we obtained a 3.16% power conversion efficiency. The device showed good reproducibility and stability over time.

Słowa kluczowe:
Electrical conductivity, Laser tracing, Bulk heterojunction polymeric solar cells, Regioregular polyalkylthiophenes, Polymer blends

Streszczenie:
Synthetic mesoporous Fe doped geoinspired nanotubes have been utilized to evaluate the modification of the surface composition, morphology charge distribution and thermal stability as functions of the Fe doping extent and Fe prevalent substitution into the octahedral or tetrahedral sites. FTIR-ATR spectroscopy analysis has allowed to highlight the chrysotile structure modification by the Fe substitution to Mg or Si and to underline clearly the crucial role of the Fe doping in the octahedral sheet in modifying chrysotile structure and morphology. XPS analysis, ζ-potentials and porosity characterization have allowed to define the propriety of the chrysotile surface structure when iron replaces Mg in octahedral or Si in tetrahedral sites. DTA analysis has allowed to relate the effect of Fe doping on the chemical–physical characteristics of both synthetic and mineral chrysotile. We have observed that the simultaneous decrease in dehydroxylation and recrystallization temperature occurs when the Fe increases on surface and this is due to the increased substitution of Fe in octahedron. The results highlight the relevance to estimate the health hazard of the natural asbestos fibres by valuating the role of Fe surface throughout the use of geoinspired chrysotile synthesised under controlled stoichiometry and structure utilizing it as a selected reference standard.

Słowa kluczowe:
Asbestos, Mesoporous synthetic chrysotile, Geoinspired inorganic nanotubes, Fe doped chrysotile, Surface functionalities

Streszczenie:
This article describes the preparation of thin films of conjugated polymers which can enhance their specific electrical conductivity by several orders of magnitude by changing their state from insulating to conducting materials. The examined polymers, i.e., a polyacetylenic and a polythiophenic derivative, are functionalized with thioalkylic side chains and are soluble in common organic solvents from which they lead to thick homogeneous films. The films can be deposited on different substrates, either rigid or flexible, and can be easily exposed to laser radiation to make them conductive. The process is irreversible, and the final conductivity is stable over time, even in the presence of high temperatures (up to 180°C), moisture, and air. The high stability of treated samples, easy polymer synthesis and quick and inexpensive suitably tailored laser tracing procedure make these materials very promising for applications in organic electronics and in the development of new electronic circuitry.

Streszczenie:
Geomimetic chrysotile nanotubes have a high potentiality in nanotechnological applications. These synthetic inorganic nanotubes can be used to prepare quantum wires with interesting electrical and optical properties. In fact, they behave as host systems, exhibiting a constant inner diameter inferior to 7 nm, a low tendency to aggregate and large inter-channel separation, preventing the interaction between individual guest filled nanomaterial acting as an unisosotropic confining structure. The chemical-physical properties of undoped and differently Fe doped geoinspired chrysotile synthetic nanotubes have been reviewed confirming that these characteristic features make synthetic chrysotile nanotubes excellent candidates to prepare innovative inorganic nanowires. Furthermore, the possibility to synthesize undoped geomimetic chrysotile nanotubes with high reproducibility and crystallinity avoids cytotoxicity, making them safe for human health.

Słowa kluczowe:
chrysotile, geomimetic nanostructures, inorganic nanotubes, nanotechnology, nanowires

Streszczenie:
Materials containing suspended micro- or nanomaterials are used extensively in multiple fields of research and industry. In order to understand the behavior of nanomaterials suspended in a liquid, the knowledge of particle stability and mobility is fundamental. For this reason, it is necessary to know the nanoscale solid-solid interaction and the hydrodynamic properties of the particles. In the presented research we used a hybrid Atomic Force Microscope coupled with Optical Tweezers system to measure the femtonewton scale interaction forces acting between single particles and the walls of a microchannel at different separation distances and environmental conditions. We show an important improvement in a typical detection system that increases the signal to noise ratio for more accurate position detection at very low separation distances.

Słowa kluczowe:
Optical Tweezers, Atomic Force Microscopy, particle-wall interaction, colloid stability

Streszczenie:
The current task of contemporary fluid mechanics evidently moves from modeling large scale turbulence to lower, molecular scale limit, where assumption of a continuous and deterministic description becomes questionable again. Once the scaling length of flow becomes comparable with structure dimensions, transport phenomena are strongly modulated by molecular interactions and its proper interpretation needs involvement of deeper physics. New experimental tools largely help in understanding transport phenomena at nanoscales. In the following review we give few examples of problems appealing for new theoretical and numerical models embracing continuous flow modeling with molecular scale phenomena.

Streszczenie:
Gaining knowledge of the solid-solid interactions and hydrodynamic and mechanical properties is crucial for understanding the processes and dynamics of molecular interactions, biological and nano- structures and also to find their future applications. Atomic force microscopy (AFM) is a versatile technique for nanoscale imaging purposes and for quantify analysis of force at the nanonewton scale. Unfortunately, due to technical limitations and restrictions related to the mechanical properties of cantilevers, this technique cannot detect small forces on the femtonewton scale and analyse the stiffness of very soft materials such as biological tissues or hydrogels. AFM is also use to manipulate materials, however, AFM-based manipulation systems are slow and imprecise. To distinguish, Optical Tweezers (OT) are scientific instruments that can trap small particles and manipulate nano- and micro-materials with much higher precision. The AFM / OT hybrid system is a high-resolution imaging instrument with a lower force limit of detection. It is capable of non-invasively manipulating of nanomaterials, single molecules and living cells, measuring forces with femtonewton accuracy, detecting motion with nanometer (10-9 m) precision and to manipulate objects, but also to obtain images directly in the same sample. The combination of AFM with Optical Tweezers will provide significant advances in biophysical research and in the study of the mechanical properties of nanomaterials [1]. In our system we combine Optical Tweezers with commercial AFM to create an instrument capable of working in hybrid mode. It allows simultaneous manipulation of biological systems of greater complexity and the analysis of their properties. Performed by us, experiments showed that AFM/OT system is a unique technique for visualization of the analysed materials, trapping single micro-objects and measure the interactions (in the range of femtonewton) between single particles. The results obtained by AFM/OT confirm that this equipment is a very useful technique also for determination the mechanical properties of very soft materials (e.g. hydrogels) [2].

Streszczenie:
Pulsatile drug delivery systems are gaining a lot of interest because of their numerous advantages, especially when compared to conventional pharmaceutical dosage forms [1]. These materials are time- and site-specific drug delivery systems which can minimize deleterious side effects of conventional drug administration systems. Nevertheless, the delivery systems that are of particular interest are the ones with reversible on-off switching capability, because they allow the delivery of therapeutic agents at the proper time after a predetermined lag time. Among the polymers used for biomedical applications, hydrogels are a class of materials of particular significance, because they can provide spatial and temporal control over the release of various types of drugs. Stimuli-responsive hydrogels can release drugs on-demand with a fast release rate through different mechanisms. The effectiveness of this process can be maximized using nanostructured materials with a large surface-area-to-volume ratio such as electrospun nanofibers. Current challenges in the development of hydrogel electrospun fibrous nanomaterials lie in the lack of spinnability of pure hydrogel precursor solutions. Addressing this issue, we firstly designed a new core-shell nanofibrous material in which the poly(N-isopropylacrylamide)-derivative hydrogel is confined within a shell of a spinnable polymer (Figure 1a). Alternatively, we developed a scaffold material in which electrospun nanofibers loaded with different bioactive molecules where surrounded by a stimuli-responsive hydrogel (Figure 1b). Morphological and chemical characterization as well as drug release studies were carried out to confirm the material’s ability to supply different doses of drugs on demand and to study the release mechanism.

Streszczenie:
Single-material organic solar cells (SMOCs) based on fullerene-grafted polythiophenes are considered promising devices for organic solar cells (OSCs). The main efforts in this field focus on the chemical tailoring of polymer molecules to reduce the side effects of charge recombination. These advances have made it possible to obtain a power conversion efficiency (PCE) close to conventional bulk heterojunction (BHJ) cells. So far, however, SMOCs still show inadequate efficiencies due to ineffective charge transport. Here we show how SMOC efficiency can be strongly increased by optimizing the supramolecular and nanoscale structure of the active layer, while achieving the highest reported efficiency value (PCE = 5.58%) [1]. The enhanced performance may be attributed to well-packed and properly oriented polymer chains. The hierarchical structure is given by the incorporation of electrospun one-dimensional nanostructures obtained from polymer chain stretching. Our results suggest that the active material optimization obtained by the use of electrospun nanofibers plays a key role in the development of efficient SMOCs.

Streszczenie:
Stimuli-responsive drug delivery systems are gaining a lot of interest due to their numerous advantages, especially when compared to conventional pharmaceutical dosage forms. One of the examples is photo stimulation that together with nanometer size agents, having high absorption in the near-infrared region, generate heat due to the interaction with light. Stimuli-responsive hydrogels with gold nanorods (AuNRs), that are used as photothermal converters, can aid in releasing drugs on-demand with a fast release rate through different mechanisms. Here we report an easy method for preparing AuNRs encapsulated in a poly(N-isopropylacrylamide) (PNIPAm) hydrogel that release water-soluble drugs due to photo stimulation. PNIPAm-AuNRs demonstrated remote, pulsatile drug release and ex vivo action after irradiation using a NIR laser. Morphological and chemical characterization as well as drug release studies were carried out to confirm the material’s ability to supply different doses of drugs on demand and to study the release mechanism. By combining the photothermal property of AuNRs and thermal-responsive effect of PNIPAm, the hydrogel shows fast thermal/photoresponse, high heating rate, high structural integrity and increased drug release due to phase change mechanism.

Słowa kluczowe:
drug delivery systems, nanofibers

Streszczenie:
Atomic force microscopy (AFM) is an evolution of scanning tunnelling microscopy that immediately gained popularity thanks to its ability to analyse nanomaterials. Initially, AFM was developed for nanomaterials imaging purposes, however the development of new features made it the most commonly used tool for studying the biophysical properties of biological samples. On the other hand, atomic force microscopy has limited use for examining sub-piconewton forces. Few techniques have been developed to measure forces below the AFM limit of detection. Among them, optical tweezers (OT) stand out for their high resolution, flexibility, and because they make it possible to accurately manipulate biological samples and carry out biophysics experiments without side effects thanks to their non-invasive properties. The combination of AFM with other techniques in the last decades has significantly extended its capability. The improvement of the AFM force resolution by developing a hybrid double probe instrument based on the combination of AFM and OT has great potential in cell or molecular biology. [1] We outline principles of atomic force microscopy combined with optical tweezers (AFM/OT) developed by our team underlying the techniques applied during the design, building and instrument use stages. We describe the experimental procedure for calibration of the system and we prove the achievement of a higher resolution (force: 10 fN – spatial: 0.1 nm – temporal: 10 ns) than the stand alone AFM. We show the use of the hybrid equipment in a number of different biophysics experiments performed employing both AFM and OT probes. The presented studies include the demonstration of simultaneous high-precision nanomanipulation and imaging, the evaluation of single biomolecule mechanical properties and the single cell membrane activation and probing. Finally, we show the further potential applications of our AFM/OT.

Słowa kluczowe:
AFM, Optical Tweezers

Słowa kluczowe:
thermal fluctuations, lateral migration, flexible filaments

Streszczenie:
Electrospun nanofibers are increasingly studied thanks to their potential applications in biomedical devices that include drug delivery systems and tissue engineering scaffolds [1]. Numerous synthetic and natural polymers were used to develop nanofibrous materials. Nanostructured materials high porosity, surface-to- volume ratio together with the ease in surface functionalization and drug incorporation, make them perfect candidates for the development of hemostats. Immediate hemorrhage management becomes crucial to preventing death and serious injury in emergency situations. Severe injuries caused by e.g. traffic accidents are the third leading cause of death worldwide [2]. Research on medical incidents of soldiers stationed in Iraq in 2003-2004 showed that the main cause of death was massive hemorrhage that led to death in about 51% of the rescued soldiers [3]. There is no universal dressing and despite the development of new hemostats, they fail in many preclinical studies. Therefore, there is a need to define most important nanofibrous material characteristics that are responsible for rapid and effective bleeding arrest. There is little research on nanostructured hemostats, regarding the impact of nanofibrous surface on blood and its components. Nonetheless, because of the wide use of nanofibres in wound dressings, artificial blood vessels as well as heart valves, there is knowledge helpful in determining material surface chemistry, wettability and other, which can affect blood coagulation. The very first findings appeared in the research where it was found that even polymers having excellent antiplatelet adhesion abilities, triggered increased platelet adhesion and activation when they were in the form of nanofibers. In several other studies, scaffold morphology, was found to have larger impact on platelet adhesion and activation than differences in the chemistry of the polymers used [4]. More specifically, it was found that materials with fiber diameter higher than 1 µm triggered higher platelet adhesion and aggregation than smaller fibers. In other research, nanofiber stiffness was assessed as more dominating than biological moieties and surface roughness of the nanofiber [5]. In spite of all, analyzed literature presents many contradictory results or findings that had low or no impact on blood clotting in research results of other groups. Hence, additional research and novel experimental methods are needed to find nano features that impact hemostat efficiency.

Słowa kluczowe:
blood-biomaterial interactions, nanofibers, clotting

Streszczenie:
Nanofibers have received considerable attention in the past years, mainly due to their vast application in medicine [1]. One of the fastest growing areas of application are wound dressings and hemostats. Among the major causes of death from trauma, massive bleeding is responsible for 30 – 40% of mortality. In the hospital, massive bleeding are the second most common cause of death (22%) just after cardiac factors (33%) [2]. Despite a large number of experiments done in the topic of blood-biomaterial interactions, coagulation mechanisms are still not fully understood. Therefore, the main objective of our work is the analysis of protein adsorption, platelet adhesion and aggregation, and blood plasma coagulation in the contact with polymer nanofibers. Various synthetic polymers, their blends with natural polymers of confirmed hemostatic effect e.g. collagen and gelatine, and additionally nanofibers made of chitosan are investigated for their potential to stop bleeding. In the final, controlled release of drugs affecting coagulation cascade will be an important step providing accelerated blood clot formation.

Słowa kluczowe:
Atomic force microscopy/optical tweezers, Nanomanipulation, Single particles analysis, Interaction force measurement, DLVO theory

Słowa kluczowe:
Hydrogel Nanofilaments, Bending Dynamics, Poiseuille Flow, Electrospinning

Streszczenie:
Atomic force microscopy (AFM) is the most commonly used method of direct force evaluation, but due to its technical limitations this single probe technique is unable to detect forces with femtonewton resolution. We present the development of a combined atomic force microscopy and optical tweezers (AFM/OT) instrument. The optical tweezers system provides us the ability to manipulate small dielectric objects and to use it as a high spatial and temporal resolution displacement and force sensor in the same AFM scanning zone. We demonstrate the possibility to develop a combined instrument with high potential in nanomechanics, molecules manipulation and biologic al studies. The presented study is aimed to quantify the interaction forces between two single polystyrene particles in the femtonewton scale by using the developed AFM/OT equipment.

Słowa kluczowe:
optical trap, nanomanipulation, femtonewtons

Streszczenie:
Mobility of hydrogel nanofilaments suspended in liquid is investigated to gain basic knowledge on hydrodynamic interactions biased by Brownian fluctuations. Typical for long macromolecules effects like spontaneous conformational changes and cross-flow migration are observed and evaluated. The collected experimental data can be used to validate assumptions present in numerical models describing intercellular transport of long biomolecules.

Słowa kluczowe:
persistence length, macromolecules, electrospinning, DNA, Brownian motion

Streszczenie:
We propose a microscale experimental model in form of highly deformable nanofilaments, which permits for precise optical measurements and to evaluate hydrodynamic interactions (mobility). The conducted research includes determination of the mechanical properties of elastic hydrogel nanofilaments obtained by electrospinning that can serve as experimental benchmark to validate theoretical and numerical models describing dynamics of long biological molecules (e.g. proteins, DNA). Nanofilaments mechanical properties are determined by studying their dynamic bending. in shear flow and deformations due to the thermal fluctuations (Brownian motion). These results are compared with AFM nanoindentation measurements. Data obtained from this research project will be a base to crea te biocompatible nanoobjects that can become tools for the regeneration of tissue (e.g. neural tissue).

Słowa kluczowe:
Biocompatible nanoobjects, highly deformable nanofilaments, regeneration of tissue

Słowa kluczowe:
electrospinning, fibres, surface, chitosan

Streszczenie:
Controlled drug delivery systems are used to improve the conventional administration of drugs. One of the main challenges is to synthesize materials able to find a defined target and to release drugs in a controlled manner [1]. Several research tasks have been focused on developing ideal drug delivery systems made by hydrogel due to their unique properties [2]. The present study is based on the idea that soft and flexible nanomaterials can easily travel in crowed environments of body fluids and biological tissues. Modification of their mechanical properties obtained by changing of the cross-linker amount may give us the possibility to tune the material rigidity according to desired application. Here, we describe a novel method based on coaxial electrospinning for obtaining highly flexible hydrogel nanofilaments able to transport and release dedicated molecules. Two different types of hydrogels (poly(N,Nisopropyl acrylamide) and polyacrylamide) with three polymer/cross-linker ratios were produced and deeply studied. The nanofilaments morphology was characterized and the release of bovine serum albumin as a function of time was quantified. Mechanical properties of highly deformable hydrogel nanofilaments were evaluated by bending dynamics and Brownian motion observation techniques. The calculated mechanical properties were compared with data obtained by nanoindention. The results highlight the crucial role of morphology and stiffness on mobility of nanofilaments colloid systems. The information gained are fundamental to design nanoobjects with well-defined chemical and physical behaviour.

Słowa kluczowe:
Nanofilaments, electrospinning, core-shell method, hydrogel

Streszczenie:
In this talk we would like to tackle general question of contemporary fluid dynamics, how far its assumption of a continuous, smooth medium remains useful when size and time scales start to approach molecular ones. The question is not trivial and seems to depend on several additional factors usually minored. For example, when full Navier-Stokes equations are replaced by their linear approximation we are loosing basic characteristics of convective motion, and still we use such approach. Once our fluid becomes granular matter with its own internal properties, proper interpretation of flow interactions with other molecular structures probably needs deeper physics. But still we try to convert such problem to the classical macro/micro scale description. Hence a general question arises, how small does a fluid have to be before it is not a fluid anymore?

Słowa kluczowe:
microfluidics, nanofluids, Brownian motion, nanofilaments

Słowa kluczowe:
Nanofilaments, hydrogel filaments, nanofibres, long nanoobjects deformability

Słowa kluczowe:
nanofilaments, hydrogel, long molecules flexibility

Słowa kluczowe:
electrospinning, flexible nanorods, Brownian motion

Słowa kluczowe:
nanomanipulation, optical trap, optical tweezers

Słowa kluczowe:
Nanoparticles, Brownian motion, hydrodynamic diameter

Słowa kluczowe:
Nanoparticles, polystyrene beads, surface properties, atomic force microscopy, hydrodynamic properties